Alkynyloxy-phenyl derivatives

ABSTRACT

Alkynyl, benzyl or phenyl, ethers and esters which are ring substituted with an oxy or a thio aliphatic chain. These ethers and esters are usful in killing and preventing the proliferation of insects by upsetting their hormonal balance.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of Ser. No. 671,453, filed Mar. 29,1976, now U.S. Pat. No. 4,051,319, which is a divisional of Ser. No.548,469, filed Feb. 10, 1975, now U.S. Pat. No. 3,957,833, which is adivisional of Ser. No. 312,074, filed Dec. 4, 1972, now U.S. Pat. No.3,880,935, which is a divisional of Ser. No. 123,060, filed Mar. 10,1971, now U.S. Pat. No. 3,718,686.

SUMMARY OF THE INVENTION

In accordance with this invention, it has been found that compounds ofthe formula: ##STR1## wherein R₁, R₃ and R₅ are methyl or ethyl; R₂ andR₄ are hydrogen or methyl; R₆ is lower alkynyl; A, B, C, D, E and F areindividually hydrogen or A and B taken together form a carbon to carbonbond or an oxygen bridge, C and D taken together form a carbon to carbonbond, and E and F taken together form a carbon to carbon bond; Z isoxygen or sulfur; Y and Y' are hydrogen, halogen, lower alkyl or loweralkoxy; X is oxygen, --CH₂ O-- or --COO--; and m, n and p are integersof from 0 to 1, with at least one of m, n and p being 1; with theproviso that when m and n are O, E and F are individually hydrogen, ortaken together form a carbon to carbon bond or an oxygen bridge; upsetthe hormone balance of pests such as insects to prevent them fromgrowing and reproducing.

The compounds of formula I are prepared by reacting a compound of theformula: ##STR2## wherein R₁, R₂, R₃, R₄, R₅, A, B, C, D, E, F, Z, Y,Y', X, m, n and p are as above and M is an alkali metal or, where X isoxygen, an alkali metal or hydrogen;

with an alkynyl halide of the formula:

    R.sub.6 --Hal                                              III

wherein R₆ is as above and Hal is a halogen.

The compounds of formula I are also prepared by reacting a halide of theformula: ##STR3## wherein R₁, R₂, R₃, R₄, R₅, A, B, C, D, E, F, Hal, m,n and p are as above;

with a compound of the formula: ##STR4## wherein R₆, X, Y, Y' and Z areas above and M' is an alkali metal or, where Z is oxygen, an alkalimetal or hydrogen.

The compounds of formula I, wherein X is ##STR5## are further preparedby reacting a compound of the formula: ##STR6## wherein R₁, R₂, R₃, R₄,R₅, A, B, C, D, E, F, Z, Y, Y', m, n and p are as above and R₇ ishydrogen, lower alkyl or aralkyl;

with an alcohol of the formula:

    R.sub.6 --OH                                               VII

wherein R₆ is as above.

In the case where, in the compound of formula I, A and B taken togetherform a carbon to carbon bond, this compound can be epoxidized to acompound of formula I wherein A and B taken together form an oxygenbridge.

DESCRIPTION OF THE PREFERRED EMBODIMENT

As used throughout this application, the term "lower alkyl" comprehendsboth straight-chain and branched-chain, saturated alkyl hydrocarbongroups having from 1 to 6 carbon atoms, such as methyl, ethyl, propyl,isopropyl, etc. As used herein, the term "lower alkoxy" comprehendsloweralkyloxy groups wherein a "lower alkyl" is defined as above, suchas methoxy, ethoxy propoxy, etc. Similarly, as used herein, the term"lower alkynyl" includes straight-chain and branched-chain,acetylenically unsaturated hydro carbon groups having from 2 to 6 carbonatoms, such as ethynyl, propargyl, butynyl, etc. As also used herein,the term "halogen" or "halo" comprehends, when not expressly statedotherwise, all four halogens, i.e., fluorine, chlorine, bromine andiodine. As further used herein, the term "alkali metal" comprehends thealkali metals of the first group of the periodic chart, such as sodiumand potassium. As still further used herein, the term "aralkyl"comprehends aryl lower alkyl groups wherein "aryl" comprehendsmono-nuclear aromatic hydrocarbons, such as phenyl, tolyl, etc., whichcan be substituted or unsubstituted in one or more positions, andpolynuclear aromatic groups, such as naphthyl phenanthyl, etc., whichcan also be substituted or unsubstituted in one or more positions, witha nitro, halo, lower alkyl or lower alkoxy substituent, and wherein"lower alkyl" is as defined above. The preferred aralkyl group isbenzene.

The compounds of formula I are useful in the control of and incombatting invertebrate animals, such as arthropods and nematodes. Thecompounds of formula I are especially useful against insects,particularly Tenebrio molitor, Tineola biselliella, Carpocapsapomonella, Leptinotarsa decemlineata, Calandra granaria, Dysdercuscingulatus and Ephestia kuhniella.

In contrast to most of the known pest-control agents which kill, disableor repell the pests by acting as contact-poisons and feed-poisons, thecompounds of formula I above prevent maturation and proliferation ofthese pests by interfering with their hormonal system. In insects, forexample, the transformation to the imago, the laying of viable eggs andthe development of laid normal eggs is distrubed. Furthermore, thesequence of generations is interrupted and the insects are indirectlykilled.

The compounds of formula I above are practically non-toxic tovertebrates. The toxicity of the compounds of formula I is greater than,1,000 mg/kg body weight. Moreover, these compounds are readily degradedand the risk of accumulation is therefore excluded. Therefore, thesecompounds can be used without fear of danger in the control of pests inanimals; plants, foods; and textiles.

Generally, in controlling invertebrate animals, the compounds of formulaI are applied to the material to be protected, e.g. foodstuffs, feeds,textiles, plants, in concentrations of from about 10⁻³ to 10⁻⁶ gm/cm² ofthe material to be protected. Generally, it is preferred to utilize thecompounds of formula I above in a composition with a suitable inertcarrier. Any conventional inert carrier can be utilized.

The compounds of formula I can, for example, be used in the form ofemulsions, suspensions, dusting agents, solutions or aerosols. Inspecial cases, the materials to be protected (e.g., foodstuffs, seeds,textiles and the like) can also be directly impregnated with theappropriate compound or with a solution thereof. Moreover, the compoundscan also be used in a form which only releases them by the action ofexternal influences (e.g., contact with moisture) or in the animal bodyitself. It is also possible to use the compounds in admixture with otherknown pesticides.

The compounds of formula I above can be used as solutions suitable forspraying on the material to be protected which can be prepared bydissolving or dispersing these compounds in a solvent such as mineraloil fractions; cold tar oils; oils of vegetable or animal origins;hydrocarbons such as napthalenes; ketones such as methyl ethyl ketone;or chlorinated hydrocarbons such as tetrachloroethylene,tetrachlorobenzene, and the like. Such sprays suitably have aconcentration of the compound of formula I of 0.01% to 5% by weight,with a concentration of 0.1% being preferred. The compounds of formula Iabove can also be prepared in forms suitable for dilution with water toform aqueous liquids such as, for example, emulsion concentrates, pastesor powders. The compounds of formula I above can be combined with solidcarriers for making, dusting or strewing powders as, for example, talc,kaolin, bentonite, calcium carbonate, calcium phosphate, etc. Thecompositions containing the compounds of formula I above can contain, ifdesired, emulsifiers, dispersing agents, wetting agents, or other activesubstances such as fungicides, bacteriacides, nematocides, fertilizersand the like. The materials which are to be protected act as bait forthe insect. In this manner, the insect, by contacting the materialimpregnated with a compound of formula I above, also contacts thecompound itself.

In accordance with this invention, representative examples of thepreferred compounds of formula I are as follows:

1-[(1,5-dimethylhexyl)oxy]-4-(propargyloxy)benzene;

1-[(3-methyl-2-butenyl)oxy]-4-propargyloxybenzene;

p-[(1,5-dimethylhexyl)oxy]-α-propargyloxytoluene;

p-[(3-methyl-2-butenyl)oxy]-α-propargyloxytoluene;

p-[(1,5-dimethylhexyl)oxy]benzoic acid propargyl ester;

p-[(3,7-dimethyl-2,6-octadienyl)oxy]benzoic acid propargyl ester;

p-[(2,3-epoxy-3-methylbutyl)oxy]benzoic acid propargyl ester

p-[(4,5-epoxy,-1,5-dimethylhexyl)oxy]benzoic acid propargyl ester;

p-[(1-ethyl-5-methyl-4-heptenyl)oxy]benzoic acid propargyl ester;

p-[(6,7-epoxy-3,7-dimethyl-2-octenyl)oxy]benzoic acid propargyl ester;

p-[(2,3-epoxy-3-methylbutyl)oxy]-α-propargyloxytoluene;

1-[(2,3-epoxy-3-methylbutyl)oxy]-4-propargyloxybenzene;

p-[(3,7,11-trimethyl-dodeca-2,6,10-trienyl)oxy]benzoic acid propargylester;

p-[(1,5-dimethyl-4-hexenyl)oxy]benzoic acid propargyl ester;

p-[(1,5-dimethylhexyl)thio]-α-propargyloxytoluene;

1-[(1,5-dimethylhexyl)oxy]-4-(propargyloxy)benzene;

p-[(1,5-dimethylhexyl)oxy]benzoic acid propargyl ester;

4-[(1,5-dimethylhexyl)oxy]-α-(propargyloxy)toluene;

p-[(4,5-epoxy-1,5-dimethylhexyl)oxy]benzoic acid propargyl ester;

p-[(1,5-dimethylhexyl)oxy]benzoic acid-2-pentynyl ester;

p-[(1,4,5-trimethylhexyl)oxy]benzoic acid propargyl ester;

p-[(1,5-dimethylhexyl)thio]benzoic acid propargyl ester;

p-[(3,6,7-trimethylocta-2,6-dienyl)oxy]benzoic acid propargyl ester;

p-[(3,6,7-trimethyloctyl)oxy]benzoic acid propargyl ester;

4-[(1,5-dimethylhexyl)oxy]-3-chlorobenzoic acid propargyl ester;

p-[(1,5-dimethylhexyl)oxy]vanillic acid propargyl ester;

3-methyl-4-[(3,7-dimethylocta-2,6-dienyl)oxy]benzoic acid propargylester;

3-bromo-4-[(6,7-dimethyl-2,6-octadienyl)oxy]-5-methoxybenzoic acidpropargyl ester; and

4-[(3,7-dimethyl-2,6-octadienyl)oxy]-3,5-dimethoxy-benzoic acidpropargyl ester.

Especially preferred are the compounds of formula I having the formula:##STR7## wherein R₁, R₂, R₅, A, B, X, Y, Y' and Z are as above.Particularly preferred are the compounds of formula Ia wherein Z isoxygen, Y is hydrogen, and A and B individually are hydrogen or takentogether form an oxygen bridge. Quite particularly preferred are thefollowing compounds of formula Ia:

1-[(1,5-dimethylhexyl)oxy]-4-propargyloxy benzene;

p-[(1,5-dimethylhexyl)oxy]benzoic acid propargyl ester;

4-[(1,5-dimethylhexyl)oxy]-α-(propargyloxy)toluene;

p-[(4,5-epoxy-1,5-dimethylhexyl)oxy]benzoic acid-propargyl ester; and

p-[(1,4,5-trimethylhexyl)oxy]benzoic acid propargyl ester.

Also especially preferred are the compounds of formula I having theformula: ##STR8## wherein R₁, R₂, R₅, A, B, E, F, X, Y, Y' and Z are asabove.

Further especially preferred compounds are the compounds of formula Iwherein R₁, R₂, and/or R₅ are methyl; R₂ and/or R₄ is hydrogen; Z isoxygen, and/or Y and Y' are hydrogen.

One method for preparing the compounds of formula I involves reacting,in a well known manner, a compound of formula II with the alkynyl halideof formula III. This reaction is suitably conducted in an inert solventand preferably in the presence of an aprotonic solvent. In carrying outthis reaction, any conventional inert organic solvent can be utilized,with benzene, toluene, dioxane, 1,2-dimethoxymethane and tetrahydrofuranbeing preferred and tetrahydrofuran being especially preferred. In thisreaction, any conventional aprotonic solvent may be utilized, withhexamethyl phosphoric acid triamide being preferred. In this reaction,temperature and pressure are not critical, and the reaction can besuitably carried out in a temperature range of 0° C. to the boilingpoint of the reaction mixture. In a preferred embodiment of thisreaction, the reaction is carried out at ca 70° C., the refluxtemperature of the especially preferred solvent.

Another method for preparing the compounds of formula I involvesreacting, in a well known manner, the compounds of formulas IV and V.This reaction is also suitably carried out in an inert solvent,preferably in the presence of an aprotonic solvent. In carrying out thisreaction, any conventional inert organic solvent can be utilized, withbenzene, toluene, dioxane, 1,2-dimethoxymethane and tetrahydrofuranbeing preferred and tetrahydrofuran being especially preferred. In thisreaction, any conventional aprotonic solvent may be utilized, withhexamethyl phosphoric acid triamide being preferred. In this reaction,temperature and pressure are not critical, and the reaction can besuitably carried out in a temperature range of 0° C. to the boilingpoint of the reaction mixture. In a preferred embodiment of thisreaction, as in the above reaction, the preferred temperature is ca 70°C.

The reaction mixtures from the reactions of either a compound of formulaII with a compound of formula III or a compound of the formula IV with acompound of formula V can be worked up in a conventional manner toobtain the compounds of formula I. A preferred method of working upincludes: pouring the reaction mixture onto ice; extracting the compoundof formula I with a conventional inert organic solvent, preferablydiethyl ether; washing the solvent extract with water; drying thesolvent and evaporating the solvent. The residual compound of formula Ican be further purified by adsorption, preferably on Kieselgel oraluminum oxide.

The above reactions of a compound of formula II, wherein M is hydrogen,with an alkynyl halide of formula III and of a compound of formula V,wherein M' signifies hydrogen, with a compound of formula IV areexpediently effected in the presence of an acid binding agent. In thesereactions, any conventional acid binding agent may be utilized. Thepreferred acid binding agents are the carbonates and organic bases, suchas pyridine, triethylamine and quinoline with the carbonates beingespecially preferred, particularly potassium carbonate. Further, inthese reactions, wherein M of the compound of formula II and M' of thecompound of formula V are hydrogen, the preferred solvents are acetoneand methyl ethyl ketone.

Still another method for preparing the compounds of formula I, involvesthe esterification of an acid of the compound of formula VI where R₇ ishydrogen with an alcohol of formula VII. In carrying out this reaction,the acid is expediently converted, initially, in an inert solvent and inthe presence of an acid binding agent into the corresponding acid halideby treatment with a halogenating agent. In this reaction, anyconventional inert organic solvent can be used, with petroleum ether,benzene and hexane being preferred solvents. Also, in this reaction, anyconventional acid binding agent, such as the organic bases, can be used,with pyridine, triethylamine, and quinoline being preferred and pyridinebeing especially preferred. Further, in this reaction, any conventionalhalogenating agent such as thionyl chloride, phosphorus trichloride,thionyl bromide, and phosphorus oxychloride can be used, with thionylchloride being preferred. In this reaction, temperature and pressure arenot critical, and the reaction may be suitably carried out at roomtemperature (25° C.).

The resulting acid halide and the alkynyl alcohol of formula VII arethen reacted in an inert solvent and in the presence of an acid bindingagent. In this reaction, any conventional inert organic solvent can beutilized with benzene, toluene, hexane, iso-octane, chloroform, carbontetrachloride and ethylene glycol dimethyl ether being preferredsolvents. Also in this reaction, any conventional acid binding agent maybe utilized, with the organic bases, such as pyridine, triethylamine andquinoline being preferred and pyridine being especially preferred. Incarrying out this reaction, temperature and pressure are not critical,and the reaction can be suitably carried out at room temperature.

Still another method for preparing the compounds of formula I involvesthe trans-esterification of a compound of formula VI wherein R₇ is alkylor aralkyl utilizing an alcohol of formula VII. This reaction isexpediently effected in an excess of the alcohol, in which case thisalcohol can also serve as the solvent. However, the reaction can also beconducted in an inert organic solvent, any conventional inert organicsolvent being suitable and the hydrocarbons, particularly benzene andtoluene, being preferred. Temperature and pressure are not critical tothis reaction, and the reaction can be expediently carried out in atemperature range between room temperature and the reflux temperature ofthe reaction mixture, with the reflux temperature being preferred. Thisreaction is preferably carried out in the presence of a catalyst such assodium, sodium methoxide, or p-toluene-sulphonic acid.

The epoxidation of a compound of formula I wherein M is 1, Z is oxygen,and A and B taken together form a carbon to carbon bond can expedientlybe carried out by treating the compound in an inert solvent with aperacid. In carrying out this reaction, any conventional inert organicsolvent may be utilized with the halogenated hydrocarbons such asmethylene chloride or chloroform being preferred. Any conventionalperacid may be utilized in this reaction. Among the preferred peracidsare perbenzoic acid, peracetic acid, pertungstic acid, performic acid,m-chloroperbenzoic acid and perphthalic acid, with m-chloroperbenzoicacid being especially preferred. In carrying out this reaction,temperature and pressure are not critical, the preferred temperaturerange being -10° C. to room temperature.

Another method for epoxidizing the compound of formula I, where M is 1,wherein Z is oxygen or sulfur, and A and B taken together form a carbonto carbon bond, involves first treating the compound with water and anN-halosuccinimide, "halo" being chlorine, bromine, or iodine, withN-bromosuccinimide being preferred to obtain a halohydrin of theformula: ##STR9## wherein R₁, R₂, R₃, R₄, R₅, R₆, C, D, E, F, X, Y, Y'Z, n and p are as above, and Hal' is chlorine, bromine or iodine. Inthis reaction, temperature and pressure are not critical, the reactionbeing preferably carried out between 0° C. and 25° C. In carrying outthis reaction, the unsaturated compound of formula I is preferablyinitially suspended in water. Then an inert organic solvent is added tothe suspension to give a homogeneous concentrated solution of thecompound of formula I in water and organic solvent. Any conventionalinert organic solvent can be utilized in this reaction, dioxane,tetrahydrofuran and 1,2-dimethoxyethane being preferred. TheN-halosuccinimide is then introduced portionwise into this homogeneoussolution to yield the halohydrin of formula VIII.

These halohydrins can then be converted by the action of a base to thecorresponding epoxide. In carrying out this reaction, any conventionalbase is suitable, with the alkali metal alkanolate being preferred,especially sodium methylate in methanol. In this reaction, temperatureand pressure are not critical, the reaction being preferably carried outbetween 0° C. and 25° C. Any conventional inert organic solvent can beutilized in this reaction, dioxane, tetrahydrofuran and1,2-dimethoxymethane being preferred.

The compounds of formulas II and VI can be obtained by first reacting acompound of formula IV with a compound of the formula: ##STR10## whereinZ, M', Y and Y' are as above; R₆ is hydrogen, hydroxymethyl, formyl or--COOR₉, and R₉ is lower alkyl, aryl or aralkyl.

This reaction can be carried out in the same manner described above forthe reaction between the compounds of formulas IV and V to yield acompound of the formula: ##STR11## wherein R₁, R₂, R₃, R₄, R₅, R₆, A-F,Y, Y', Z, m, n and p are as above.

The compound of formula X, wherein R₆ is formyl or --COOR₉, is thenreduced to a compound of the formula: ##STR12## wherein R₁, R₂, R₃, R₄,R₅, A-F, Y, Y', Z, m, n and p are as above and R₆ ' is --CH₂ OH.

Alternatively, the compound of formula X, wherein R₆ is --COOR₉, is thensaponified or the compound of formula X, wherein R₆ is formyl, is thenoxidized to a compound of the formula: ##STR13## wherein R₁, R₂, R₃, R₄,R₅, A-F, Y, Y', Z, m, n and p are as above and R₆ " is --COOH.

The compound of formula X, wherein R₆ is formyl or --COOR₉, can beconverted to the compound of formula XI, wherein R₆ is --CH₂ OH, byreduction. This reduction reaction can be carried out in a conventionalmanner with a metal hydride, such as an alkali metal hydride, in aninert organic solvent. In carrying out this reaction, any conventionalmetal hydride can be used, with the preferred hydrides being mixed metalhydrides, particularly sodium borohydride or lithium aluminum hydride,and alkylated metal hydrides, particularly, dialkyl aluminum hydrides.Especially preferred hydrides are di-isobutyl aluminum hydride andbis-(methoxy-ethyleneoxy) sodium aluminum hydride. In this reaction, anyconventional, inert organic solvent can be used, with the preferredsolvents being: the alkanols, especially methanol, in the presence ofsodium borohydride; the ethers, especially tetrahydrofuran or dioxane,in the presence of lithium aluminum hydride; and the ethers and thehydrocarbons, especially hexane, benzene or toluene, with the alkylatedmetal hydrides, particularly di-isobutyl aluminum hydride. Also, incarrying out this reaction, temperature and pressure are not critical,with a temperature range of -20° C. to 50° C. being preferred.

The compound of formula X, wherein R₆ is --COOR₉ can be converted to thecompound of formula XII, wherein R₆ ' is --COOH, by saponification. Thissaponification reaction can be carried out in a conventional mannerusing an alkali metal hydroxide, such as sodium or potassium hydroxide.In carrying out this reaction, temperature and pressure are notcritical, and the reaction can be carried out at elevated temperature.In this reaction, any conventional inert solvent which dissolves boththe alkali metal hydroxide and the compound of formula X may be utilizedwith diethylene glycol/water or methanol/water (1:1) being preferred.

The compound of formula X, wherein R₆ is formyl, can be converted to thecompound of formula XII, wherein R₆ " is --COOH, by oxidation. Thisoxidation reaction can be carried out in a conventional manner usingsilver oxide. In carrying out this reaction temperature and pressure arenot critical, and the reaction can be carried out at room temperature.The silver oxide, preferably Ag₂ O, is preferably formed in situ in anaqueous solution of silver nitrate and caustic soda (NaOH). Thisreaction is carried out in water or in an organic solvent miscible withwater. Any conventional organic solvent miscible with water may be used,with the following solvents being preferred: the lower alcohols,particularly methanol, ethanol and isopropanol; the ethers,particularly, 1,4-dioxane; and the ether alcohols, particularly2-methoxy-ethanol and 2-ethoxy-ethanol.

When the compounds of formulas X, XI, and XII, wherein Z is oxygen, areunsaturated, they can, if desired, be hydrogenated in a conventionalmanner by, for example, hydrogenating in the presence of a conventionalhydrogenation catalyst. In carrying out this reaction, temperature andpressure are not critical, a temperature range between about 25° C. andthe boiling temperature of the reaction mixture and atmospheric orelevated pressures being preferred. Suitable as hydrogenation catalystsare, for example, Raney-nickel or preferably the noble metals, withpalladium and platinum being especially preferred. Suitable as solventsare acetic acid ethyl ester and the alkanols such as methanol andethanol.

When the compounds of formulas X, XI, and XII, are unsaturated, theycan, if desired, be epoxidized in the same manner described above forthe epoxidation of the compounds of formula I.

The compounds of formula X, wherein R₆ is hydroxy or hydroxymethyl, offormula XI wherein R₆ ' is --CH₂ OH and of formula XII, wherein R₆ " is--COOH, can be directly converted to the alkali metal salt of formulaII. This reaction can be expediently effected by treatment with analkali metal hydride, alkali metal alcoholate or an alkali metalhydroxide, sodium being the preferred alkali metal. The reaction ispreferably carried out in the presence of an inert organic solvent. Anyconventional inert organic solvent may be utilized, with dioxane,tetrahydrofuran, dimethylformamide or diethyl ether being the preferredsolvents with an alkali metal hydride, with a lower alkanol, especiallymethanol, being the preferred solvent with an alkali metal alcoholate,and with methanol, ethanol, acetone or the like being the preferredsolvent with an alkali metal hydroxide.

In the species of the compounds of formulas I, II, IV, VI, X, XI and XIIof this invention, wherein the side-chain is unsaturated or epoxidized,these species exist as a cis/trans isomer mixture. The isomer mixturecan be separated into the all cis or all trans isomers in a conventionalmanner by, for example, gas chromatography.

By this method, the isomer mixture is dissolved in an inert organicsolvent, hexane, diethyl ether or acetic acid ethyl ester beingpreferred solvents, and then adsorbed on Kieselgel. The isomers adsorbedin different zones can be eluted with one of the aforesaid solvents orsolvent mixtures and isolated.

The isomer mixtures can, in individual cases, also be separated byfractional distillation methods or possibly also by fractionalcrystallization methods.

The following examples illustrate the invention. All temperatures arestated in degrees centigrade. The inert gas atmosphere is nitrogen. Theterm "hexane/15% acetic ester" as used in Examples 5 and 41 encompassesa solution consisting of 85% hexane and 15% ethyl acetate (by volume).The term "70% bis(2-methoxy-ethoxy) sodium aluminium hydride" as used inExample 27 comprehends a benzenic solution of 70% by weight ofbis(2-methoxy-ethoxy) sodium aluminium hydride. The term "80% by weightm-chlorperbenzoic acid" as used in Examples 31, 33 and 34 means that them-chlorperbenzoic acid contains 20% m-chlorbenzoic acid and that thepercentage of m-chloroperbenzoic acid present in the mixture wasdetermined by titration in the usual manner.

EXAMPLE 1

11.8 g of a 50% by weight suspension of sodium hydride in mineral oil iswashed twice in an inert gas atmosphere with 50 ml of tetrahydrofuraneach time and then added to 150 ml of tetrahydrofuran. A solution of36.5 g of hydroquinone monopropargyl ether dissolved in 80 ml oftetrahydrofuran is then added dropwise to the sodium hydride mixture.47.5 g of 2-bromo-6-methylheptane in 80 ml of hexamethyl phosphoric acidtriamide is subsequently added dropwise to the mixture. The reactionmixture is heated under reflux conditions for 2 hours, then cooled,poured onto ice and exhaustively extracted with diethyl ether. The etherextract is washed with water, dried over sodium sulfate and evaporatedunder reduced pressure. The residual, oily,1-[(1,5-dimethylhexyl)oxy]-4-(propargyloxy)-benzene is purified byadsorption on Kieselgel; B.P. 150°-152° C./1 mmHg.

EXAMPLE 2

By utilizing the procedure of Example 1, by reacting hydroquinonemonopropargyl ether with 3-methyl-2-butenyl bromide, there is obtained1-[(3-methyl-2-butenyl)oxy]-4-propargyloxy-benzene; B.P. 145°-148° C./1mmHg.

EXAMPLE 3

By utilizing the procedure of Example 1 by reacting syringic acidpropargyl ester with geranyl bromide, there is obtained4-[(3,7-dimethyl-2,6-octadienyl)oxy]-3,5-dimethoxy benzoic acidpropargyl ester; n_(D) ²¹ = 1.5320

EXAMPLE 4

By utilizing the procedure of Example 1, by reacting 5-bromovanillicacid propargyl ester and geranyl bromide, there is obtained3-bromo-4-[(6,7-dimethyl-2,6-octadienyl)oxy]-5-methoxybenzoic acidpropargyl ester; n_(D) ²⁸ = 1.5440.

EXAMPLE 5

43.5 of a 50% by weight suspension of sodium hydride in mineral oil iswashed twice in an inert gas atmosphere with 100 ml of tetrahydrofuraneach time and then, added to 150 ml of tetrahydrofuran. A solution of100 g of hydroquinone in 100 ml of tetrahydrofuran is added dropwise tothe sodium hydride mixture. 108 g of propargyl bromide in 150 ml ofhexamethyl phosphoric acid triamide is subsequently added dropwise tothe mixture. The reaction mixture is heated under reflux conditions for2 hours, then cooled, poured onto ice and exhaustively extracted withdiethyl ether. The ether extract is washed with water, dried over sodiumsulfate and evaporated under reduced pressure. The residual mixture isseparated by chromatography on Kieselgel. Hydroquinone dipropargyl etheris eluted with 10% acetic ester. M.P. 50° C. With hexane/15% aceticester there is eluted hydroquinone monopropargyl ether. B.P. 100°-102°C./1.0 mmHg.

EXAMPLE 6

By utilizing the procedure of Example 5, by reacting syringic acid andpropargyl bromide, there is obtained syringic acid propargyl ester, F.P.105°-106° C.

EXAMPLE 7

By utilizing the procedure of Example 5, by reacting 5-bromovanillicacid with propargyl bromide, there is obtained 5-bromovanillic acidpropargyl ester; M.P. 121°-122° C.

EXAMPLE 8

4.0 g of a 50% by weight suspension of sodium hydride in mineral oil iswashed twice in an inert gas atmosphere with 25 ml of tetrahydrofuraneach time and then, added to 100 ml of tetrahydrofuran. A solution of20.6 g of p-[(1,5-dimethylhexyl)oxy] benzoic acid in 100 ml oftetrahydrofuran is then added dropwise to the sodium hydride mixture. 10g of propargyl bromide in 40 ml of hexamethyl phosphoric acid triamideis subsequently added dropwise to the mixture. The reaction mixture isheated under reflux conditions for 2 hours, then cooled poured onto iceand exhaustively extracted with diethyl ether. The ether extract iswashed with water, dried over sodium sulfate and evaporated underreduced pressure. The residual oily p-[(1,5-dimethylhexyl)oxy]benzoicacid propargyl ester is purified by adsorption on Kieselgel; B.P.207°-210° C./1 mmHg.

EXAMPLE 9

By utilizing the procedure of Example 8, by reactingp-farnesyloxybenzoic acid with propargyl bromide, there is obtainedp-farnesyloxybenzoic acid propargyl ester; B.P. 245°-250° C./0.1 mmHg.

EXAMPLE 10

By utilizing the procedure of Example 8, by reactingp-[(1,5-dimethyl-4-hexenyl)oxy]benzoic acid with propargyl bromide,there is obtained p-[(1,5-dimethyl-4-hexenyl)oxy]benzoic acid propargylester; n_(D) ²² = 1.5252.

EXAMPLE 11

By utilizing the procedure of Example 8, by reactingp-[(3,7-dimethyl-2,6-octadienyl)oxy]benzoic acid with propargyl bromide,there is obtained p-[(3,7-dimethyl-2,6-octadienyl)oxy]benzoic acidpropargyl ester; B.P. 135°-137° C./0.01 mmHg.

EXAMPLE 12

By utilizing the procedure of Example 8, by reactingp-[(3,6,7-trimethylocta-2,6-dienyl)oxy]benzoic acid with propargylbromide, there is obtainedp-[(3,6,7-trimethylocta-2,6-dienyl)oxy]benzoic acid propargyl ester;n_(D) ²⁴ = 1.5349.

EXAMPLE 13

By utilizing the procedure of Example 8, by reactingp-[(1,5-dimethylhexyl)oxy]-3-chlorobenzoic acid with propargyl bromide,there is obtained 4-[(1,5-dimethylhexyl)oxy]-3-chlorobenzoic acidpropargyl ester; n_(D) ²⁶ = 1.5155.

EXAMPLE 14

By utilizing the procedure of Example 8, by reactingp-[(1,5-dimethylhexyl)oxy]vanillic acid with propargyl bromide, there isobtained p-[(1,5-dimethylhexyl)oxy]vanillic acid propargyl ester; n_(D)²⁴ = 1.5151.

EXAMPLE 15

By utilizing the procedure of Example 8, by reactingp-[(1,4,5-trimethylhexyl)oxy]benzoic acid with propargyl bromide, thereis obtained p-[(1,4,5-trimethylhexyl)oxy]benzoic acid propargyl ester;n_(D) ²² = 1.5050.

EXAMPLE 16

By utilizing the procedure of Example 8, by reactingp-[(1,5-dimethylhexyl)oxy]benzoic acid with 1-bromo-2-pentyne, there isobtained p-[(1,5-dimethylhexyl)oxy]benzoic acid-2-pentynyl ester; n_(D)²⁴ = 1.5078.

EXAMPLE 17

By utilizing the procedure of Example 8, by reactingp-[(1-ethyl-5-methyl-4-heptenyl)oxy]benzoic acid with propargyl bromide,there is obtained p-[(1-ethyl-5-methyl-4-heptenyl)oxy]benzoic acidpropargyl ester; n_(D) ²¹ = 1.5200.

EXAMPLE 18

By utilizing the procedure of Example 8, by reacting3-methyl-4-[(3,7-dimethylocta-2,6-octadienyl)-oxy]-benzoic acid withpropargyl bromide, there is obtained3-methyl-4-[(3,7-dimethylocta-2,6-dienyl)oxy]benzoic acid propargylester; n_(D) ²⁸ = 1.5331.

EXAMPLE 19

13.7 g of a 50% suspension of sodium hydride in mineral oil is washedtwice in an inert gas atmosphere with 70 ml of tetrahydrofuran each timeand then, added to 100 ml of tetrahydrofuran. A solution of 40 g ofp-hydroxybenzoic acid methyl ester in 250 ml of tetrahydrofuran is thenadded dropwise to the sodium hydride mixture. 50 g of2-bromo-6-methylhept-5-ene in 80 ml of hexamethyl phosphoric acidtriamide is subsequently added dropwise to the mixture. The reactionmixture is heated under reflux conditions for 2 hours, poured onto iceand exhaustively extracted with diethyl ether. The ether extract iswashed with water, dried over sodium sulfate and evaporated underreduced pressure. The residual oilyp-[(1,5-dimethyl-4-hexenyl)oxy]benzoic acid methyl ester is purified byadsorption on Kieselgel; n_(D) ²⁵ = 1.5109.

EXAMPLE 20

By utilizing the procedure of Example 19, by reacting p-hydroxybenzoicacid methyl ester with 2-bromo-6-methyl heptane, there is obtainedp-[(1,5-dimethylhexyl)oxy]benozic acid methyl ester; B.P. 132°-134°C./0.1 mmHg.

EXAMPLE 21

By utilizing the procedure of Example 19, by reacting p-hydroxybenzoicacid methyl ester with 2-bromo-5,6-dimethyl heptane, there is obtainedp-[(1,4,5-trimethylhexyl)oxy]benzoic acid methyl ester; n_(D) ²⁵ =1.4938.

EXAMPLE 22

By utilizing the procedure of Example 19, by reacting p-hydroxybenzoicacid methyl ester with 3-bromo-7-methylnon-6-ene, there is obtainedp-[(1-ethyl-5-methyl-4-haptenyl)oxy]benzoic acid methyl ester; B.P.202°-205° C./12 mmHg.

EXAMPLE 23

By utilizing the procedure of Example 19, by reacting3-methyl-4-hydroxybenzoic acid methyl ester with1-bromo-3,7-dimethyl-2,6-octadiene, there is obtained3-methyl-4-[(3,7-dimethyl-2,6-octadienyl)oxy]benzoic acid methyl ester;n_(D) ²⁸ = 1.5248.

EXAMPLE 24

7.2 g of p-[(1,5-dimethyl-hex-4-enyl)oxy]-benzoic acid methyl ester isdissolved in 30 ml of 2-N aqueous caustic soda, diluted with 50 ml of anaqueous solution of 50% by volume methanol and heated under reflux for11/2 hours. The reaction solution is then cooled, treated with 200 ml ofwater and exhaustively extracted with diethyl ether. The alkalineaqueous phase is acidified with 2-N hydrochloric acid and exhaustivelyextracted with diethyl ether. The latter ether extract is dried oversodium sulfate and evaporated under reduced pressure. The residualp-[(1,5-dimethylhex-4-enyl)oxy]benzoic acid is purified bycrystallization from benzene; M.P. 57°-59° C.

EXAMPLE 25

By utilizing the procedure of Example 24, the following acids can beobtained from their corresponding methyl esters:

p-[(1,5-dimethylhexyl)oxy]benzoic acid; M.P. 55° C.;

p-[(3,7,11-trimethyl-dodeca-2,6,10-trienyl)oxy]benzoic acid; M.P.80°-81° C.;

p-[(3,7-dimethyl-2,6-octadienyl)oxy]benzoic acid; M.P. 118°-120° C.;

p-[(3,6,7-trimethylocta-2,6-dienyl)oxy]benzoic acid; M.P. 128°-129° C.;

p-[(1,5-dimethylhexyl)oxy]-3-chlorobenzoic acid; n_(D) ²⁶ = 1.5231;

p-[(1,5-dimethylhexyl)oxy]vanillic acid; M.P. 69°-70° C.;

p-[(3-methyl-2-butenyl)oxy]benzoic acid; M.P. 153°-154° C.;

p-[(1,4,5-trimethylhexyl)oxy]benzoic acid; n_(D) ²¹ = 1.5082;

p-[(1-ethyl-5-methyl-4-heptenyl)oxy]benzoic acid; n_(D) ²¹ = 1.4891; and

3-methyl-4-[(3,7-dimethyl-2,6-octadienyl)oxy]benzoic acid; F.P. 93°-94°C.

EXAMPLE 26

4.1 g of a 50% by weight suspension of sodium hydride in mineral oil iswashed twice in an inert gas atmosphere with 25 ml of tetrahydrofuraneach time and then, added to 50 ml. of tetrahydrofuran. A solution of 20g of p-[(1,5-dimethylhexyl)oxy]benzyl alcohol in 100 ml oftetrahydrofuran is then added dropwise to this mixture. 10.3 g propargylbromide in 40 ml of hexamethyl phosphoric acid triamide is subsequentlyadded dropwise to the mixture. The reaction mixture is heated underreflux conditions for 2 hours, then cooled, poured onto ice andexhaustively extracted with diethyl ether. The ether extract is washedwith water, dried over sodium sulfate and evaporated under reducedpressure. The residual oilyp-[(1,5-dimethylhexyl)oxy]-α-propargyloxytoluene is purified byadsorption on Kieselgel; B.P. 170°-175° C./1.0 mmHg.

EXAMPLE 27

42 g of p-[(1,5-dimethylhexyl)oxy]benzoic acid methyl ester is dissolvedin 250 ml of benzene and, with stirring, treated dropwise with 50 g of70% bis(2-methoxy-ethoxy)sodium aluminum hydride. The reaction solutionis further stirred at 25° C. for 5 hours and thereafter treated withwater. The organic phase is separated off, dried under sodium sulfate,carefully filtered (using a filter aid) and evaporated under reducedpressure. There is obtained a residual ofp-[(1,5-dimethylhexyl)oxy]benzyl alcohol; B.P. 180°-182° C./1.0 mmHg.

EXAMPLE 28

By utilizing the procedure of Example 26, by reactionp-[(3-methyl-2-butenyl)oxy]benzyl alcohol with propargyl bromide, thereis obtained 1-[(3-methyl-2-butenyl)oxy]-4-propargyloxy-toluene; B.P.146°-149° C./1 mmHg.

EXAMPLE 29

10.1 g of a 50% by weight suspension of sodium hydride in mineral oil iswashed twice in an inert gas atmosphere with 50 ml of tetrahydrofuraneach time and then, introduced into 100 ml of tetrahydrofuran. Asolution of 32 g of p-hydroxybenzoic acid methyl ester in 200 ml oftetrahydrofuran is then added dropwise to the sodium hydride mixture.40.5 g of 1-bromo-3-methylbut-2-ene in 80 ml of hexamethyl phosphoricacid triamide is subsequently added dropwise to the mixture. Thereaction mixture is heated under reflux conditions for 2 hours, thencooled, poured onto ice and exhaustively extracted with diethyl ether.The ether extract is washed with water, dried over sodium sulfate andevaporated under reduced pressure. The residual oilyp-[(3-methyl-2-butenyl)oxy]benzoic acid methyl ester is purified byadsorption on Kieselgel. M.P. 45°-46° C.

By utilizing the procedure of Example 27,p-[(3-methyl-2-butenyl)oxy]benzoic acid methyl ester is converted intop-[(3-methyl-2-butenyl)oxy]benzyl alcohol; M.P. 41°-42° C.

EXAMPLE 30

2.2 g of 50% by weight suspension of sodium hydride in mineral oil iswashed twice in an inert gas atmosphere with 25 ml of tetrahydrofuraneach time and then added to 30 ml of tetrahydrofuran a solution of 9.9 gof p-[(2,3-epoxy-3-methylbutyloxy)benzoic acid in 100 ml oftetrahydrofuran is then added dropwise to the sodium hydride mixture 5.5g of propargyl bromide in 20 ml of hexamethyl phosphoric acid triamideis subsequently added dropwise to the mixture. The reaction mixture isheated under reflux conditions for 2 hours, then cooled, poured onto iceand exhaustively extracted with diethyl ether. The ether extract iswashed with water, dried over sodium sulfate and evaporated underreduced pressure. The residual oilyp-[(2,3-epoxy-3-methylbutyloxy)benzoic acid propargyl ester is purifiedby adsorption on Kieselgel; M.P. 80°-81° C.

EXAMPLE 31

3.9 g of p-[(1,5-dimethyl-hex-4-enyl)oxy]benzoic acid propargyl ester isdissolved in 150 ml of methylene chloride. The solution is treateddropwise at 0° C. with a solution of 3.0 g of 80% by weightm-chloroperbenzoic acid in 100 ml of methylene chloride. After 15 mins.,the reaction mixture is successively washed with an aqueous solution of2% by weight sodium bisulphite with an aqueous solution of 5% by weightsodium bicarbonate and with water. The organic phase is separated off,washed over sodium sulphate and evaporated under reduced pressure. Theresidual p-[(4,5-epoxy-1,5-dimethylhexyl)oxy]benzoic acid propargylester is purified by adsorption on Kieselgel; B.P. 120°-123° C./0.05mmHg.

EXAMPLE 32

By utilizing the procedure of Example 31, 2.0 g ofp-[(3,7-dimethyl-2,6-octadienyl)oxy]benzoic acid propargyl ester isconverted into p-[(6,7-epoxy-3,7-dimethyl-2-octenyl)oxy]benzoic acidpropargyl ester; n_(D) ²⁴ = 1.5362.

EXAMPLE 33

1.15 g of p-[(3-methyl-2-butenyl)oxy]-α-propargyloxy-toluene isdissolved in 40 ml of methylene chloride and cooled to 0° C. (ice-bathcooling). 1.5 g of 80% by weight m-chloroperbenzoic acid is addedportionwise to this mixture and the solution is thereafter stirred at 0°C. for 2 hours. The mixture is worked up as follows: diluted with 350 mlof methylene chloride; washed with ice-cold 1-N caustic soda; washedwith saturated aqueous sodium chloride solution; dried over sodiumsulfate; and evaporated. By chromatography on Kieselgel, there isobtained p-[(2,3-epoxy-3-methylbutyloxy]-α-propargyloxy-toluene; B.P.120°-123° C./0.1 mmHg.

EXAMPLE 34

6.4 g of 1-[(3-methyl-2-butenyl)oxy]-4-propargyloxy-benzene is dissolvedin 80 ml of methylenechloride and cooled to 0° C. (ice-bath cooling).7.15 g of 80% by weight m-chloroperbenzoic acid is added portionwise tothis mixture and the solution is thereafter stirred at 0° C. for 2hours. The mixture is worked up as follows: diluted with 350 ml ofmethylene chloride; washed with ice-cold 1-N caustic soda; washed withsaturated aqueous sodium chloride solution; dried over sodium sulfate;and evaporated. By chromatography on Kieselgel, there is obtained1-[(2,3-epoxy-3-methylbutyl)oxy]-4-propargyloxy-benzene; M.P. 72°-73° C.

EXAMPLE 35

By utilizing the procedure of Example 26, by reactingp-[(1,5-dimethylhexyl)thio]benzyl alcohol with propargyl bromide, thereis obtained p-[(1,5-dimethylhexyl)thio]-α-propargyloxy-toluene; n_(D) ²⁹= 1.5243.

EXAMPLE 36

By utilizing the procedure of Example 27,p-[(1,5-dimethylhexyl)thio]benzoic acid methyl ester is converted intop-[(1,5-dimethylhexyl)thio]benzyl alcohol; n_(D) ²⁹ = 1.5270.

EXAMPLE 37

By utilizing the procedure of Example 19, by reacting p-thio benzoicacid methyl ester with 2-bromo-6-methylheptane, there is obtainedp-[(1,5-dimethylhexyl)-thio]benzoic acid methyl ester; B.P. 168°-170°C./0.5 mmHg.

EXAMPLE 38

By utilizing the procedure of Example 8, by reactingp-[(1,5-dimethylhexyl)thio]benzoic acid and propargyl bromide, there isobtained p-[(1,5-dimethylhexyl)thio]benzoic acid propargyl ester M.P.130°-131° C./0.03 mmHg.

EXAMPLE 39

By utilizing the procedure of Example 24,p-[(1,5-dimethylhexyl)thio]benzoic acid methyl ester is converted intop-[(1,5-dimethylhexyl)thio]benzoic acid; M.P. 63°-65° C.

EXAMPLE 40

By utilizing the procedure of Example 8, by reactingp-[(3,6,7-trimethyloctyl)oxy]benzoic acid with propargyl bromide, thereis obtained p-[(3,6,7-trimethyloctyl)oxy]benzoic acid propargyl esters;B.P. 153°-154° C./0.05 mmHg.

EXAMPLE 41

5 g of p-[(3,6,7-trimethylocta-2,6-dienyl)oxy]benzoic acid is dissolvedin 20 ml of acetic ester and hydrogenated under normal pressure and at atemperature of about 25° C. in the presence of 0.2 g of platinum oxide.The hydrogenation is terminated after the uptake of 2 mols of hydrogen,and the catalyst is filtered off from the reaction mixture. The clearsolution is evaporated under reduced pressure. The residualp-[(3,6,7-trimethyloctyl)oxy]benzoic acid is purified by crystallizationfrom petroleum ether; M.P. 89°-90° C.

EXAMPLE 42

10 g of p-[(1,5-dimethylhexyl)oxy]benzoic acid is heated to 70° C. with20 ml of thionyl chloride for 10 mins. The clear yellow-colored solutionis evaporated at 50° C. under water-jet pump vacuum. After the additionof 40 ml of propargyl alcohol, the mixture is heated to 70° C. for 15min. After evaporation in water-jet pump vacuum, the residue ischromatographed on Kieselgel, yielding p-[(1,5-dimethylhexyl)oxy]benzoicacid propargyl ester; B.P. 207°-210° C./1.0 mmHg.

EXAMPLE 43

10 g of p-[(1,5-dimethylhexyl)oxy]benzoic acid methyl ester, 30 ml ofpropargyl alcohol and 0.5 g of sodium methoxide are heated to reflux for1/2 an hour. The excess propargyl alcohol is thereupon slowly (5 hrs.)distilled off. The residue is poured onto water and extracted withdiethyl ether. The ether solution is dried with sodium sulfate andevaporated. The dark-yellow p-[(1,5-dimethylhexyl)oxy]benzoic acidpropargyl ester obtained is purified over kieselgel.

EXAMPLE 44

13 g of p-[(1,5-dimethylhexyl)oxy]benzoic acid methyl ester is heated toreflux with 9 g of propargyl alcohol and 0.1 g of p-toluenesulphonicacid. The excess propargyl alcohol is thereupon slowly (5 hrs.)distilled off. The residue is poured onto water and extracted withdiethyl ether. The ether phase is dried with sodium sulfate andevaporated. There is obtained dark-yellowp-[(1,5-dimethylhexyl)oxy]benzoic acid propargyl ester which is purifiedon Kieselgel.

The experiments described in the following examples are carried out withthe following representative examples of the propargyloxy derivatives ofthis invention as the active substances.

(I) p-[(1,5-dimethylhexyl)oxy]-α-propargyloxytoluene

(II) p-[(1,5-dimethylhexyl)oxy]benzoic acid propargyl ester

(III) p-[(1,5-dimethyl-4-hexenyl)oxy]benzoic acid propargyl ester

(IV) 1-[(2,3-epoxy-3-methylbutyl)oxy]benzoic acid propargyl ester

(V) 1-[(1,5-dimethylhexyl)oxy]-4-(propargyloxy)benzene

(VI) 1-[(2,3-epoxy-3-methylbutyl)oxy]-4-(propargyloxy)-benzene.

EXAMPLE 45

2 filter paper discs [24 cm² ] are sprayed with an acetonic solution ofthe active substance, and after drying, the discs together with anuntreated paper disc and with a paper disc soaked only with acetone, areeach so fixed together that there is formed a tunnel for the shelter of10 cockroaches (Blattella germanica) each. The cockroaches are in thelast larval stage. They remain in permanent contact with the treatedpaper and are provided with water and food.

The development of the larvae set out is registered daily. 100%disturbance of metamorphosis: A normal animal develops from none of thelarvae

    ______________________________________                                               Amount of          Number Number                                              active    Number   of     of                                           Active substance of       normal normal Activity                              substance                                                                            10.sup.-x g/cm.sup.2                                                                    larvae   imagos animals                                                                              %                                     ______________________________________                                        I      10.sup.-4 10        1     5      83                                    Control with acetone                                                                       10       10       --     --                                      Control with acetone                                                                       10       10       --     --                                      ______________________________________                                    

EXAMPLE 46

A disc of cotton material [10 cm² ] is sprayed with an acetonic solutionof the active substance, and after drying, the disc, together with anuntreated disc of material and a disc of material soaked only withacetone, are each occupied by 30-60 freshly laid eggs of the meal moth(Ephestia kuhniella). The disc is placed in a cage and held at 25° C.and 90% rel. humidity.

The development of the eggs is registered over a few days. 100%mortality of the eggs: No development of the embryos in the eggs layedon discs of material soaked with active substance.

    ______________________________________                                                Amount of                                                                     active     Number    Number                                           Active  substance  of        of      Mortality                                substance                                                                             10.sup.-x g/cm.sup.2                                                                     eggs      larvae  %                                        ______________________________________                                        I       10.sup.-5  32        0       100                                              10.sup.-6  33        0       100                                      II      10.sup.-5  32        0       100                                              10.sup.-6  30        0       100                                      III     10.sup.-4  40        0       100                                              10.sup.-5  36        0       100                                              10.sup.-6  36        0       100                                      IV      10.sup.-5  47        0       100                                              10.sup.-6  33        0       100                                      V       10.sup.-5  44        0       100                                              10.sup.-6  34        0       100                                      Control with acetone                                                                         50        50         0                                         Control with acetone                                                                         49        46         6                                         ______________________________________                                    

EXAMPLE 47

A disc of woollen material [10 cm² ] is sprayed with an acetonicsolution of the active substance, and the disc, together with anuntreated disc of material and a disc of material soaked only withacetone, are each hung in a cage occupied by 20 young cloths moth(Tineola biselliella).

The development of the eggs layed at 25° C. is registered for 4 days.100% sterilant action: larvae hatch from none of the eggs laid ontreated and untreated discs of woollen material. 100% ovicidal action:larvae hatch from none of the eggs laid on treated discs of woollenmaterial.

    ______________________________________                                                      Amount of                                                                     active    Sterilant                                                           substance action   Ovicidal action                              Active substance                                                                            10.sup.-x g/cm.sup.2                                                                    %        %                                            ______________________________________                                        VI            10.sup.-3 0        100                                                        10.sup.-4 0        100                                          Control with acetone    0         0                                           Control with acetone    0         0                                           ______________________________________                                    

EXAMPLE 48

A filter paper strip [90 cm² ] is sprayed with an acetonic solution ofthe active substance and, after drying, the strip, together with anuntreated paper strip and a paper strip soaked only with acetone, areeach occupied by 3-4 pairs of freshly moulted images of the cotton bug(Dysdercus cingulatus).

The development of the eggs laid daily is registered. 100% mortality ofthe eggs: no development of the embryos in the eggs laid on stripssoaked with active substance.

    ______________________________________                                                Amount of                                                                     active                                                                Active  substance  Number of Number of                                                                             Mortality                                substance                                                                             10.sup.-x g/cm.sup.2                                                                     eggs      larvae  %                                        ______________________________________                                        I       10.sup.-5  380       --      100                                              10.sup.-6   50       --      100                                      II      10.sup.-5  430       --      100                                      III     10.sup.-5  311        4       99                                      IV      10.sup.-5  392        60      83                                      Control with acetone                                                                         270       262        3                                         Control with acetone                                                                          41       390        5                                         ______________________________________                                    

EXAMPLE 49

1 g of p-[(3-methyl-2-butenyl)oxy]-α-(2-propynyloxy)toluene wasdissolved in a mixture of 80 ml of dioxane and 40 ml of water. To thissolution there was added under cooling with ice (10° C.) portionwise0.85 g of N-bromosuccinimide. After this addition the mixture wasstirred at room temperature for 15 hours and then diluted with 80 ml ofwater. Thereafter 2.5 g of sodium sulfite are added and the solutionexhaustively extracted with ether. The combined ether extracts werewashed with water, dried over sodium sulfate and evaporated. Bychromatography on Kieselgel with hexane/ethyl acetate (85:15 parts byvolume) there was obtainedp-[(3-bromo-2-hydroxy-3-methylbutyl)oxy]-α-(2-propynyloxy)toluene. n_(D)²² : 1.5374.

We claim:
 1. A compound of the formula ##STR14## wherein A, B, C, D, E,and F are individually hydrogen, or A and B taken together form a carbonto carbon bond, C and D taken together form a carbon to carbon bond, Eand F taken together form a carbon to carbon bond; R₁, R₃ and R₅ aremethyl or ethyl;Y and Y¹ are hydrogen, halogen, lower alkyl or loweralkoxy; R₂ and R₄ are hydrogen or methyl; R₆ is lower alkynyl; and m, nand p are integers of from 0 to 1; with at least one of m, n and p being1; with the proviso that A, B, C, D, E and F are not all hydrogen. 2.The compound of claim 1 having the formula: ##STR15## wherein R₁, R₂,R₅, A, B, E, F, Y, Y' Z and X are as above.
 3. The compound of claim 2wherein E and F are a carbon to carbon bond.
 4. The compound of claim 3wherein said compound is p-[(3,7-dimethyl2,6-octadienyl)-oxy]benzoicacid propargyl ester.
 5. The compound of claim 2 wherein A and B takentogether are a carbon to carbon bond and E and F taken together are acarbon to carbon bond.
 6. The compound of claim 5 wherein said compoundis 4-[(3,7-dimethyl-2,6-octadienyl)-oxy]-3,5-methoxy-benzoic acidpropargyl ester.